CN104620068B9 - 用于借助于蒸馏分离包含二氧化碳的混合物的方法和设备 - Google Patents

用于借助于蒸馏分离包含二氧化碳的混合物的方法和设备 Download PDF

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CN104620068B9
CN104620068B9 CN201380014046.2A CN201380014046A CN104620068B9 CN 104620068 B9 CN104620068 B9 CN 104620068B9 CN 201380014046 A CN201380014046 A CN 201380014046A CN 104620068 B9 CN104620068 B9 CN 104620068B9
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A·布里格利亚
A·达德
F·洛克伍德
X·特拉维萨
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Abstract

本发明涉及一种用于通过蒸馏分离包含二氧化碳的气体的方法。根据本方法，包括至少50％的二氧化碳的气体在第一交换器(43)中冷却以便产生冷却的流体，将从冷却的流体得到的液体(23)发送至蒸馏塔(25)以便在其中分离，顶部气体(6)被从蒸馏塔提取出并且在第一交换器中被再加热，将比包含至少50％的二氧化碳的气体更富含二氧化碳的底部液体(27)提取出并且该底部液体的至少一部分在第一交换器中被加热，底部液体的至少第一部分在第一交换器中蒸发以便产生蒸发的部分，该蒸发的部分(31)被传送回蒸馏塔，NOx去除塔被供给液化的循环气体，该循环气体通过使来自塔的底部液体蒸发和再液化而产生。

Description

用于借助于蒸馏分离包含二氧化碳的混合物的方法和设备
技术领域
本发明涉及一种用于通过包括移除NOx的级的蒸馏来分离包括二氧化 碳的混合物的方法和设备。
背景技术
已知的是，通过蒸馏分离包括作为主要成分之一的二氧化碳的混合物。 所有涉及纯度的百分比均为摩尔百分比。
混合物可包括至少50％的二氧化碳，甚至于至少70％的二氧化碳并且 甚至于至少90％的二氧化碳。气体的剩余物/其余部分可包括下列气体的至 少一种：氮气、氧气、氩气或氢气。混合物可从富氧燃烧过程中产生，在 该富氧燃烧过程中氧气和燃料的混合物在锅炉中燃烧产生废气，本发明的 待分离的混合物组成净化后产生的废气的至少一部分。
富含二氧化碳的流体可包括至少80％的二氧化碳，甚至于至少95％的 二氧化碳。
采用蒸馏来净化混合物的大多数此类型的方法使用蒸馏塔，该蒸馏塔 的底部通过待蒸馏的混合物被加热。
在US-A-3 498 067、DE-A-3639779和JP-A-56077673的情况下，将混 合物发送至蒸馏塔，对于文献FR-A-2 934 170、EP-A-1 953 486、 US20020059807、US-A-3 130 026、WO2006054008、WO2007126972、 EP-A-0 965 564和EP-A-0 994 318，底部液体在专门的交换器中与混合物 相互作用而蒸发，在用于冷却该混合物的另一更大的交换器中分离。
US-A-4 441 900描述了一种用于通过蒸馏分离包含二氧化碳的气体的 方法。
发明内容
根据本发明，提供一种用于通过蒸馏分离包括二氧化碳的气体的方法， 其中：
i)包括至少50％的二氧化碳的气体在第一交换器中冷却以便产生冷却 的流体；将从冷却的流体得到的液体发送至蒸馏塔以便在其中分离，
ii)顶部气体被从蒸馏塔取出并且在第一交换器中被再加热，
iii)将比包括至少50％的二氧化碳的气体更富含二氧化碳的底部液体 取出并且底部液体的至少一部分在第一交换器中被再加热，
iv)底部液体的至少第一部分在第一交换器中蒸发以便产生蒸发的部 分并且蒸发的部分返回至蒸馏塔，
v)将底部液体的第二部分发送至第一交换器，在第一交换器中该第二 部分被再加热并且蒸发并且由此形成的气体被压缩以便形成富含二氧化碳 的气态产品，
vi)对形成循环气体的压缩气体的一部分执行冷却和可选地冷凝；所 述部分随后在第一交换器中冷却，其至少一部分降低压力并且返回到第一 交换器中蒸发以便形成制冷循环，以及
vii)通过将冷却的流体发送至用于去除NOx的塔、从该塔取得顶部气 体并将其发送至至少一个相分离器并且在相分离器中的一个中取得液体而 从冷却的流体得到液体，其特征在于，用于去除NOx的塔为汽提塔，在该 汽提塔顶部用液化的循环气体供给该汽提塔。
根据其他可选的特征：
–在第一交换器中再加热的顶部气体的至少一部分与包括二氧化碳的 气体在第一交换器的上游混合，
–通过将冷却的流体发送至至少一个相分离器并且从相分离器中的一 个中取得液体而从冷却的流体得到液体，
–来自相分离器中的一个的气体在第一交换器中被再加热并且在涡轮 (19F、19G)中降低压力，
–所述气体从富氧燃烧锅炉产生并且来自用于去除NOx的塔的底部液 体返回至锅炉。
根据本发明的另一主题，提供一种用于通过蒸馏分离包括至少50％的 二氧化碳的气体的设备，该设备包括：冷却气体以便产生冷却的流体的第 一交换器；用于从冷却的流体得到液体的装置；蒸馏塔；用于将从冷却的 流体得到的液体发送至蒸馏塔的管道；用于从蒸馏塔取出顶部气体的顶部 气体管道，该顶部气体管道连接至第一交换器以便在第一交换器中再加热 顶部气体或从顶部气体得到的气体；用于取出相对于该气体富含二氧化碳 的底部液体的液体管道，该液体管道连接至第一交换器以便在第一交换器 中再加热该液体；连接至第一交换器并且连接至蒸馏塔以便使蒸发的液体 返回至蒸馏塔的管道；用于将底部液体的第二部分发送至第一交换器(其 在第一交换器中被再加热和蒸发)的管道；用于压缩由此形成的气体以便 形成富含二氧化碳的气态产品的压缩机；用于冷却和可选地冷凝形成循环 空气的压缩气体的一部分的装置；用于将冷却的压缩气体的所述部分发送 至第一交换器的装置；用于降低至少一部分冷却的压缩空气的压力并且用 于使其返回到第一交换器中蒸发以便形成制冷循环的降压装置；用于去除 NOx的塔；用于将冷却的液体发送至用于去除NOx的塔的管道；包括至少 一个相分离器、用于得到液体的装置；用于从用于去除NOx的塔取出顶部 气体并且用于将该顶部气体发送至至少一个相分离器的管道；用于使液体 从相分离器中的一个离开的管道，其特征在于，用于去除NOx的塔为汽提 塔，并且其中，所述设备包括在该汽提塔顶部用液化的循环气体供给该汽 提塔的管道。
根据其它可选的主题，所述设备包括：
–用于使在第一交换器中被再加热的顶部气体的至少一部分与包括二 氧化碳的气体在第一交换器的上游混合的装置(例如，相遇的两个管道)，
–用于将冷却的流体发送至至少一个相分离器的管道和用于将相分离 器的一个中的液体发送至蒸馏塔的管道，
–用于发送来自相分离器中的一个的气体以便在第一交换器中再加热 的管道、涡轮和用于将经再加热的气体发送至涡轮的管道，
–至少一个相分离器、用于将冷却的流体发送至相分离器的管道和用于 将从冷却的流体得到的液体从相分离器发送至塔的管道，
–用于源自相分离器的气体的涡轮膨胀机，
–被供给冷却的流体并连接至相分离器以便产生液体的用于去除NOx 的塔，所述相分离器连接至蒸馏塔。
根据本发明的另一主题，提供一种富氧燃烧设备，该设备包括富氧燃 烧锅炉，用于将气体从锅炉发送至根据权利要求6至9中任一项所述的设 备的管道和用于将底部液体从用于去除NOx的塔发送至锅炉的管道。
附图说明
下面结合图1至3和图4更详细地描述本发明，图1至3示出对照例 设备，图4示出根据本发明的设备。
在这些附图中，用于分离二氧化碳和氧气或一氧化碳的塔不包括底部 再沸器，底部液体仅在设备的主交换器中蒸发，在该主交换器中来自蒸馏 塔的顶部气体被再加热。
具体实施方式
图1中，包括二氧化碳和氧气或一氧化碳的湿气体1在压缩机3中被 压缩。此压缩机3包括四个级3A、3B、3C、3D，每个级后面为冷却装置 5A、5B、5C、5D。在冷却装置5D中冷却之后，气体1由冷却器5E冷却 以便形成气体7，然后(将气体7)发送至净化单元9以便移除水分。所形 成的干燥气体11在第一交换器43中冷却，在第一交换器43中干燥气体 11冷却并且部分地冷凝。部分冷凝的气体被发送至相分离器13。来自相分 离器13的液体被发送至阀21以便形成液体23，该液体23在蒸馏塔25的 顶部进给至该蒸馏塔25。
富含氧气和/或一氧化碳的气体6从塔的顶部取出并且发送至冷却器 5D的上游。可选地，它可返回至产生气体1的富氧燃烧单元。
富含二氧化碳的来自蒸馏塔25的底部液体27被发送至第一交换器 43，在此处蒸发以便形成流31，该流31在阀中降低压力之后返回蒸馏塔 25的底部。
底部液体的剩余物/其余部分29并不在交换器中加热而是与循环流体 59混合。所形成的混合物分成三个部分。部分37通过阀41将压力降低至 低压，在第一交换器43中蒸发并且然后在压缩机47中压缩。部分35通过 阀39将压力降低至中压，在第一交换器43中蒸发并且然后由压缩机45 压缩。部分33在没有降低压力的情况下在第一交换器43中蒸发并且然后 与所述两个经压缩的部分混合。由此形成的混合物49在压缩机51中压缩、 冷凝并且然后分成两部分。部分56由泵53加压以便形成液体产品。剩余 物55在第一交换器43中冷却，在阀57中降低压力并且与流29混合以便 作为制冷循环返回至第一交换器43。
来自相分离器13的气体15在第一交换器43中再加热以便形成流17， 该流17由再热器5F、5G再加热并且通过串联的两个涡轮19F、19G降低 压力以便形成压力降低的流19。
在图2中，与图1不同的是，底部液体27的部分61通过完全穿过第 一交换器43而蒸发和再加热以便作为流61被发送至压缩机47的下游，该 流61被发送至压缩机47的下游。这个可选的形式特别有利，因为这避免 了使在蒸馏塔的压力下蒸发的液体过冷(特别是如果流33被降低至零)； 因此，这会减轻交换器的冷端的负担并且改善液化能。这会因为过冷仅在 液体压力降低时才会被证实存在，因为此时转换成蒸气的部分减少，甚至 于没有。
在图3中，与图2不同的是，蒸发的液体61的部分63没有在交换器 43中冷却、而是在阀62中降低压力之后返回至蒸馏塔25的底部。此可选 的形式特别有利于控制再沸气体的温度。
还可以将底部液体27分成至少两部分，一部分在交换器43中蒸发， 然后返回至蒸馏塔25，另一部分(可选地剩余部分)在第二蒸馏塔中处理 以便生产富含二氧化碳的产品。
图4示出这样的情况，其中该方法使得可以在塔25的分离的上游利用 专门的塔125使混合物净化去除NO。该专门的塔125是用于去除NOx的 塔。用于去除NOx的塔使得能够降低进入塔的气体的NO和/或NO2和/或 N2O的含量。包括二氧化碳和氧气或一氧化碳的湿气体1在压缩机3中被 压缩。此压缩机3包括四个级3A、3B、3C、3D，每个级后面为冷却装置 5A、5B、5C、5D。在冷却装置5D中冷却之后，气体1由冷却器5E冷却 以便形成气体7，然后(将气体7)发送至净化单元9以便移除水分。所形 成的干燥气体11在第一交换器43中冷却并且然后在交换器43的中间位置 取出以便发送至塔125的底部。塔125为没有底部再沸器或顶部冷凝器的 简单的塔。其充当汽提塔以便使气体11净化去除NOx。富含NO的液体 127在塔125的底部取出并且被发送至为气体1来源的锅炉或者被储存。 经净化除去NOx的气体113从塔125的顶部离开，在交换器43中冷却并 且部分地冷凝。将部分冷凝的气体发送至相分离器13。将来自相分离器13 的液体发送至阀21以便形成液体23，该液体23在蒸馏塔25的顶部进给 蒸馏塔25。
富含氧气和/或一氧化碳的气体6从塔的顶部取出并且发送至冷却器 5D的上游。可选地，该气体6可返回至产生气体1的富氧燃烧单元。可通 过渗透或其他手段分离此气体以便形成待重新加热的其他气体。
富含二氧化碳的来自蒸馏塔25的底部液体27被发送至第一交换器 43，在第一交换器43中蒸发以便形成流31，该流31在阀中降低压力后返 回蒸馏塔25的底部。
底部液体的部分29与流体59混合并且然后分成三部分。部分37通过 阀41将压力降低至低压，在第一交换器43中蒸发并且然后在压缩机47 中压缩。部分35通过阀39将压力降低至中压，在第一交换器43中蒸发并 且然后由压缩机45压缩。部分33在没有降低压力的情况下在第一交换器 43中蒸发并且然后与所述两个经压缩的部分混合。由此形成的混合物49 在压缩机51中压缩、冷凝并且然后分成两部分。部分56由泵53加压以便 形成液体产品。剩余物55在第一交换器43中冷却并且分成两个部分。部 分59在阀57中降低压力并且与流29混合以便作为制冷循环返回至第一交 换器43。
另一部分155在阀157中降低压力并且然后以液态方式输送至用于移 除NOx的塔125的顶部。
来自相分离器的气体15在第一交换器43中再加热以便形成流17，该 流17由再热器5F、5G再加热并且通过串联的两个涡轮19F、19G降低压 力以便形成压力降低的流19。

Claims (10)

1.一种用于通过蒸馏分离包含二氧化碳的气体的方法，其中：
i)包含至少50％的二氧化碳的气体在第一交换器(43)中冷却以便产 生冷却的流体；从该冷却的流体得到的液体(23)被发送至蒸馏塔(25) 以便在其中分离，
ii)从蒸馏塔抽取顶部气体并且该顶部气体或从该顶部气体得到的气体 在第一交换器中被再加热，
iii)比所述包含至少50％的二氧化碳的气体更富含二氧化碳的底部液 体(27)被抽取出并且该底部液体的至少一部分在第一交换器中被再加热，
iv)所述底部液体的至少第一部分在第一交换器中蒸发以便产生蒸发 的部分并且该蒸发的部分(31)返回至蒸馏塔，
v)所述底部液体的第二部分被发送至第一交换器，该第二部分在第一 交换器中被再加热和蒸发并且由此形成的气体被压缩以便形成富含二氧化 碳的气态产品，
vi)对形成循环气体的压缩气体的一部分执行冷却；所述部分随后在 第一交换器(43)中冷却，其至少一部分降低压力并且返回到第一交换器 中蒸发以便形成制冷循环，以及
vii)通过将冷却的流体发送至用于去除NOx的塔(125)、从所述塔 抽取顶部气体并将其发送到至少一个相分离器(13)并且在相分离器中的 一个中抽取液体(23)而从冷却的流体获得液体，其特征在于，所述用于 去除NOx的塔为汽提塔，在所述汽提塔的顶部被供应液化的循环气体。
2.根据权利要求1所述的方法，其特征在于，在第一交换器(43) 中再加热的顶部气体的至少一部分与包含二氧化碳的气体在第一交换器的 上游混合。
3.根据权利要求1所述的方法，其特征在于，来自相分离器(13) 中的一个的气体在第一交换器中被再加热并且在涡轮(19F、19G)中降低 压力。
4.根据权利要求1所述的方法，其特征在于，所述包含至少50％的 二氧化碳的气体从富氧燃烧锅炉产生并且来自所述用于去除NOx的塔 (125)的底部液体返回至锅炉。
5.根据权利要求1所述的方法，其特征在于，对所述形成循环气体 的压缩气体的一部分执行冷凝。
6.一种用于通过蒸馏分离包含至少50％的二氧化碳的气体的设备， 该设备包括冷却气体以便产生冷却的流体的第一交换器(43)；用于从冷 却的流体得到液体的装置(13、125)；蒸馏塔(25)；用于将从冷却的流 体得到的液体发送至蒸馏塔的管道；用于从蒸馏塔抽取顶部气体的顶部气 体管道，该顶部气体管道连接至第一交换器以便在第一交换器中再加热顶 部气体或从顶部气体得到的气体；用于抽取相对于所述包含至少50％的二 氧化碳的气体富含二氧化碳的底部液体(27)的液体管道，该液体管道连 接至第一交换器以便在第一交换器中再加热所述底部液体；连接至第一交 换器并且连接至蒸馏塔以便使蒸发的液体返回至蒸馏塔的管道；用于将底 部液体的第二部分(29)发送至第一交换器的管道，所述底部液体的第二 部分在第一交换器中被再加热和蒸发；用于压缩由此形成的气体以便形成 富含二氧化碳的气态产品的压缩机(45、47、51)；用于冷却形成循环气 体的压缩气体的一部分的装置；用于将冷却的压缩气体的所述部分发送至 第一交换器(43)的装置；用于降低至少一部分冷却的压缩空气的压力并 且用于使该部分冷却的压缩空气返回到第一交换器中蒸发以便形成制冷循 环的降压装置；用于去除NOx的塔(125)；用于将冷却的液体发送至用 于去除NOx的塔的管道；由至少一个相分离器(13)组成、用于获得液体 的装置；用于从用于去除NOx的塔抽取顶部气体并且用于将该顶部气体发 送到至少一个相分离器(13)的管道；用于使液体(23)从相分离器中的 一者离开的管道，其特征在于，用于去除NOx的塔为汽提塔，并且其中， 所述设备包括在顶部用液化的循环气体供给该汽提塔的管道。
7.根据权利要求6所述的设备，其特征在于，包括用于使在第一交 换器(43)中被再加热的顶部气体的至少一部分与包含二氧化碳的气体在 第一交换器的上游混合的装置。
8.根据权利要求6或7所述的设备，其特征在于，包括用于发送来 自相分离器(13)中的一者的气体以便在第一交换器中再加热的管道、涡 轮(19F、19G)和用于将经再加热的气体发送至涡轮的管道。
9.根据权利要求6所述的设备，其特征在于，所述用于冷却形成循 环气体的压缩气体的一部分的装置用于使所述形成循环气体的压缩气体的 一部分冷凝。
10.一种富氧燃烧设备，包括富氧燃烧锅炉，用于将气体从锅炉发送 至根据权利要求6至9中任一项所述的设备的管道和用于将底部液体从用 于去除NOx的塔发送至锅炉的管道。
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EP2932177B1 (fr) 2017-09-06
PL2932177T3 (pl) 2017-12-29
FR2988167A1 (fr) 2013-09-20
US20150059402A1 (en) 2015-03-05
WO2013135993A3 (fr) 2015-09-11
CN104620068B (zh) 2017-03-01
EP2932177A2 (fr) 2015-10-21
AU2013234166A1 (en) 2014-10-02
AU2013234166B2 (en) 2017-05-18
CA2865991A1 (fr) 2013-09-19
CN104620068A (zh) 2015-05-13
US9903648B2 (en) 2018-02-27
FR2988167B1 (fr) 2018-06-15
CA2865991C (fr) 2020-01-14

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